GB2129370A - Laminated packaging films and their use - Google Patents
Laminated packaging films and their use Download PDFInfo
- Publication number
- GB2129370A GB2129370A GB08329340A GB8329340A GB2129370A GB 2129370 A GB2129370 A GB 2129370A GB 08329340 A GB08329340 A GB 08329340A GB 8329340 A GB8329340 A GB 8329340A GB 2129370 A GB2129370 A GB 2129370A
- Authority
- GB
- United Kingdom
- Prior art keywords
- laminated film
- film according
- layer
- heat
- copolyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006280 packaging film Polymers 0.000 title description 6
- 239000012785 packaging film Substances 0.000 title description 6
- 239000010410 layer Substances 0.000 claims description 45
- 229920001577 copolymer Polymers 0.000 claims description 12
- 238000003466 welding Methods 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 235000013305 food Nutrition 0.000 claims description 8
- 239000012793 heat-sealing layer Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000002365 multiple layer Substances 0.000 claims description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 235000021485 packed food Nutrition 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 229940117958 vinyl acetate Drugs 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229920003620 Grilon® Polymers 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- 229920003182 Surlyn® Polymers 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000009928 pasteurization Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920003941 DuPont™ Surlyn® 1652 Polymers 0.000 description 1
- 229920006055 Durethan® Polymers 0.000 description 1
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- 229920010048 Novamid® 2020A Polymers 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920003300 Plexar® Polymers 0.000 description 1
- 229920006097 Ultramide® Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- -1 eg. Substances 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IPEHBUMCGVEMRF-UHFFFAOYSA-N pyrazinecarboxamide Chemical compound NC(=O)C1=CN=CC=N1 IPEHBUMCGVEMRF-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005493 welding type Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/08—PVDC, i.e. polyvinylidene chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
- Y10T428/1331—Single layer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
- Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
- Y10T428/1345—Single layer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31728—Next to second layer of polyamide
- Y10T428/31732—At least one layer is nylon type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
- Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
Landscapes
- Laminated Bodies (AREA)
- Wrappers (AREA)
Description
1
SPECIFICATION Laminated packaging films and their use
GB 2 129 370 A 1 This invention relates to laminated packaging films useful, for example, for making bags and pouches, and especially suitable for packaging food products. In the description which follows, the term "packaging materials" refers both to films utilized as such and to bags or other preformed containers 5 manufactured from such films.
Amide homopolymers have been used for several years as components in several types of laminated packaging films, on account of their good mechanical and optical properties, and satisfactory gas barrier capabilities. However, such homopolymers have inferior heat shrinking and welding properties. For these reasons amide homopolymers have been used primarily for non-shrinkable laminated films, in combination with various types of welding layers.
A forward step in the field of amide films has been made with the commercial introduction of a new family of polyamide copolymers obtained using various types and amounts of comonomers.
However, the use of such polyamide copolymers, hereinafter termed copolyamides, in the preparation of films intended for packaging applications, is made problematical, because the gas barrier 15 properties, which, as mentioned, are satisfactory in the case of amide homopolymers, are in this case so weak that the films are no longer impervious to gas. Thus, copolyamides, are used heretofore as backing or "structural" layers to impart strength, required the addition to the laminate of further gas barrier layers and welding layers of various types.
In conventional laminates, whether or not they include a structural layer of copolyamide, polyolefins 20 are generally used for welding or sealing layers which are characterized by low melting points and poor resistance to high temperatures. Thus, and especially in the instance of food products requiring such high temperature heat treatments as sterilization, pasteurization, or cooking, the treatments had to be carried out prior to packaging, with the evident disadvantage that the treated product had to undergo further handling and attendant risk of contaminating it.
Accordingly, while it has been highly desirable to have packaging films available which could withstand high temperature treatment, such that pre-packaged food products can be subjected to thermal treatment, this has been impossible heretofore with conventional films currently in use owing to the poor resistance to heat of the welding layers employed thus far.
The present invention provides a packaging material, particularly intended for food product 30 applications, which has high mechanical characteristics in combination with superior resistance to thermal treatment, even when carried out for extended periods of time and at high temperatures.
Packaging film in accordance with the invention has excellent welding properties and is highly resistant to the thermal and mechanical stresses involved in the welding process. It also possesses desirable heat shrinking properties, and good wear resistance.
The heat-shrinkable multiple-layer laminated film of the present invention comprises at least one surface layer including copolyamides obtained by random copolymerization of precursor monomers of at least two different polyamides, said copolyamides having melting points, measured for example on a Perkin Elmer DSC-2 device, in the 1200C to 2401C range. Such films are especially useful for making bags and other containers for packaging food products, at least a portion of the said container being 40 formed by heat welding together two sections of a laminated film according to the invention through their respective heat sealing layers. Such containers are capable of withstanding, without suffering damage to the heat weld, heat treatment at temperatures in the range of 700C to 1200C for a period of time, which varies inversely with the temperature, from about 10 minutes to about 15 hours.
This invention is based upon the surprising finding that copolyamides may be used in laminated 45 film as surface layers to perform as heat-welding, wear-resistant layers, and as such afford considerable advantages hitherto unattainable with conventional heat- shrinkable laminate films having polyolefinic heat welding layers.
Tests carried out on various types of packages, using each time different thickness dimensions, number, arrangement, or composition of the various layers, have shown that the provision of a copolyamide heat sealing layer in the laminated film affords packages which are resistant to prolonged heat treatment at high temperatures, without prejudice to the integrity of both the welds and film itself, and without the film component layers delaminating or wrinkling.
The copolyamides useful in this invention are obtained by random copolymerization of precursor monomers of at least two different polyamides. As is known, polyamides either derive from the 55 polymerization of a single type of monomer comprising both the chemical functions which are typical of polyamides, i.e. amino and acid groups, such monomers being typically lactams, or from the polycondensation of two types of polyfunctional monomer, i.e. polyamines and polybasic acids.
In the preparation of the copolyamides for use in this invention, therefore, two different lactams maybe employed, or two types of polyamines and polyacids, or a lactam on one side and a polyamine 60 and a polyacid on the other.
Thus, the copolyamides which are suitable for use with this invention may be prepared from monomers selected from caprolactam, lauryllactam, w-aminoundecanoic acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, terephthalic acid, dodecanedioic acid, hexamethylene diamine, or p- 2 GB 2 129 370 A xylylenedia mine. Such copolyamides as are currently available commercially may be used, e.g., those known under the following trademarks: GRILON CA 6 (a Nylon 6/12 containing about 38% of 12, and having a melting range of 135-1451C) and GRILON CR 9 (a Nylon 6/12 containing about 14% of 12 and having a melting range of 197-2001C) (both from EMS Chemie), ULTRAMID C 35 (a nylon 6/6-6 containing about 19% of 6-6 and having a melting range ofl 87- 2000C) (from BASF), 5 DURETHAN C 38 F (from Bayer), and NOVAMID 2030 and NOVAMID 2020A (from Mitsubishi). Such copolyamides desirably have melting points in the 120C to 2401C range.
Expediently, the copolyamides acting as the heat sealing layer are employed in the new laminated films in association with additional layers of various character and in varying number, depending on the specific requirements which the final film is to meet in relation with its intended application.
In particular for use in films intended for packaging food products such as meat, hams, etc., the heat sealing copolyamidic layer may be associated with a backing or structural (or filler) layer capable of imparting the strength required for the application, as well as with a layer having good gas barrier properties.
The gas barrier layer may comprise any polymer conventionally utilized for that purpose, such as a 15 copolymer of ethylene/vinyl alcohol (EVOH), polyvinylidene-chloride (PVDC), or a copolymer thereot For the structural or backing layer, any material possessed of good strength properties may be used, e.g. an olefinic polymer or copolymer.
An example of simple structure for a laminated film processed in accordance with this invention is the following:
copolyamide/EVOH/copolyamide.
For very high temperature applications, the adherence of the gas barrier layer to the polyolefinic layers must be inadequate, in which case adhesives can be interposed between the various layers constituting the laminated film.
Examples of laminated films according to the invention which have more than three layers are the 25 following:
INSIDE OUTSIDE (1) Copolyamide/Adhesive/Filler/PVDC/Protective layer, or (2) Copolyamide/1 st adhesive/2nd adhesive/PVDC/3rd adhesive/Protective layer wherein the "inside" layer is that devised to contact the food product during packaging application and 30 to be heat sealed.
In these exemplary films, the filler and protective layers may comprise low-cost olefinic materials having good bonding properties for PVDC, e.g. a copolymer of ethylene/vinyl acetate (EVA) having a vinyl acetate content of 3 to 30% and a melt flow index of 0.2 to 20. The filler layer may also comprise a polymer not necessarily having good adhesion to PVDC, eg., ethylene or propylene homo- or copolymers.
The adhesive layers may comprise modified olefinic copolymers, such as modified EVA like those available commercially under the trademarks PLEXAR (from CHEMPLEX), ADMER (from MITSUI), OREVAC (from ATO CHEMIE), CXA and SURLYN (from DU PONT), LUPOLEN (from BAS), NOVATEC (from MITSUBISHI), ethylene/ethyl acrylate copolymers (from BP), or copolymers of ethyle ne/methyl acryl ate or ethylene/acrylic acid.
The film (2) exemplified above may be suitable for very high temperature applications, where the adherence between PVDC and the filler layers on one side, and the protective one on the other side, may be inadequate and may require the use of several adhesives.
The laminated films of this invention which comprise copolyamide heat sealing layers are 45 especially heat resistant. In particular, the same resistance to heat is also exhibited by the weld made from the heat sealing layers of the invention, where the film is formed into a bag, pouch or other container, or utilized as such and subsequently wrapped around a product and welded thereon.
Thus, unlike conventional films which can withstand a heat shrinking treatment up to a maximum of about 961C for no more than 1-2 seconds, bags formed from the new laminated film can withstand 50 a pasteurization treatment at 951C for periods of about 1 hour, a sterilization treatment at about 120'C for periods up to 10 minutes, and a cooking treatment in the prepackaged form at 701C for periods up to 14 hours.
If a copolyamide layer of appropriate thickness, in the range from 3 to 50 m is used, laminate films are obtained which are not only highly resistant to heat treatment but also have extremely good 55 properties of wear and abrasion resistance.
In fact, it has been found that the copolyamide layer utilized in this invention has, in addition to excellent characteristics as the inside heat-sealing layer, also good wear, abrasion and puncture resistance properties.
Alternatively, for the high wear-resistant layers, additional copolyamidic layers may be used, in particular as outer layers. In that case, the copolyamide heat sealing layer would have a thickness dimension reduced by 3 It, resistance to wear being afforded by at least one further copolyamidic outer :c GB 2 129 370 A 3 layer having a thickness of 10 to -100 y. Of course, there can be also provided more copolyamide layers in addition to the two mentioned above, because, as explained, the laminated film of this invention may be made-in. an unlimited number of variations and,with a number of layers which is only limited by considerations of convenience in manufacturing and use. By orienting the laminated films of this invention or the individual layers composing it, and then laminating said layers, films are obtained 5 which exibit excellent heat shrinking properties.
The new laminated film may be produced by conventional techniques, by extruding the layers which compose the film, and then causing them to adhere together, and/or by tubular co-extrusion thereof, and subsequent stretching and orientation, e.g. in a blown up bubble, so as to obtain a heat shrinkable film.
Articles of manufacture, for example bags and other containers can be formed from the laminated films using any suitable technique. For example a tubular co-extruded film may be flattened, transversely heat sealed and severed to produce end-seal bags. Bags can also be prepared, which are side-seal bags, by starting from the tubular flattened -film, slitting it along one side, making pairs of transverse heat seals and then severing into bags by separating between the pair of transverse seals.
The heat shrinkability of the films of the invention has been shown to be quite satisfactory, as outlined above, and capable of meeting the requirements of the packaging application for which the film is intended.
The transparency of the copolyamide layer, due to the less crystalline nature of such compounds, makes the film ideally suitable for packaging products which are to remain in full view.
The examples which follow illustrate some of the more important aspects of the invention.
EXAMPLE 1
Bags were prepared by heat welding films according to the invention and then testqd. The structure of the bags and results of the tests are shown in Table 1 below.
TABLE 1
2 3 Structure Ny CA 6 Ny CA6ISU /EVA 18% Ny CA6/SU/Ny CA6 Thickness 35 ft 34 It 19 p 29 it 32 p 11 p 25 p Shrinkage at 800C % T 39 L 36 T 40 L 46 T 39 L 39 at 850C % 40 38 44 48 46 46 at 950C % 55 50 49 54 50 54 VPHB at 800C IOWP(Cm) 60(152) 80(203) 90(229) at 850C IOWP(cm) 55(140) 70(178) 84(213) at 95"C IOWP(cm) Film breaks 60(152) 55(140) VPHS with fat at 80"C IOWP(cm) 54(137) 80(203) 90(229) at 8511C IOWP(cm) 52(132) 70(178) 80(203) at 95C IOWP(cm) Film breaks 55(140) 50(127) Resistance to heat:
at 701C x 14 h good good at 95C x I h good good at 120C x 10 min. good good Bag dimensions (mm) 180 x 360 180 x 360 180 x 360 IOWP: inch H20 4 GB 2 129 370 A 4 where:
Ny CA6 is a copolyamide produced by EMS-CHEMIE; SU is Surlyn, a registered trademark of DuPont for ionomeric resins of their production; EVA is a copolymer of ethylene/vinylacetate having an 18% content by weight of vinylacetate; VPHB is a method developed by the Applicants for evaluating the hot strength of the weld 5 (variable pressure hot burst). The variable pressure hot burst (VPHB) method comprises immersing in hot water a sample (bag) on which a heat seal has been formed, injecting air under increasing pressure (measured in inches or cm of water pressure) and measuring the pressure at which the heat seal breaks.
The values shown give the pressure, expressed as inch (or cm) H20, whereat the weld falls. By comparison, commercially currently available heat shrinkable bags reach values in the 10 to 20 inch (25 10 to 50 cm) range.
Column 1 of the Table shows the properties of a single-layer copolyamide film suitable for use in the laminated films of this invention.
It may be seen from Table 1 that bags formed from films in accordance with this invention (Columns 2 and 3) have excellent heat resisting properties. Moreover, they show good heat shrinking and gas barrier properties.
EXAMPLE 2
Wear and abrasion resistance tests carried out on experimental heat shrinkable bags, such as one made of a laminate having an overall thickness of 130 microns, having ceramic tureens packaged therein, have shown a reject percent, as evaluated after transportation on a truck over distances equal 20 to or exceeding 1,000 km, equal to about 50% less than the rejects resulting from the use of bags having the same thickness and currently used.
A suitable laminate may made, using the technique generally described in USP 4273549, by coating on to a known heat-shrinkable laminate as described in British Specification No. 1392334, sold by the Applicants under the trade name BB-1, and having layers of irradiated ethylene/vinyl acetate 25 copolymer, polyvinylidene chloride, and ethylene/vinyl acetate copolymer, further layers of Surlyn 1652 (as adhesive) and Grilon CA6.
Claims (15)
1. A heat shrinkable multi-layer laminated film comprising at least one surface layer including a copolyamide obtained by random copolymerization of precursor monomers of at least two different 30 polyamides, said copolyamide having a melting point in the range of 1200C to 2400C.
2. Laminated film according to claim 1 wherein the said surface copolyamide layer is a heat sealing layer.
3. Laminated film according to claim 1 or 2, wherein the said polyamide precursor monomers are selected from caprolactam, lauryllactam, (o-aminoundecanoic acid, adipic acid, azelaic acid, sebacic 35 acid, undecanedioic acid, terephthalic acid, dodecanedioic acid, hexamethylenedia mine and p xylylenediamine.
4. Laminated film according to claim 1, 2 or 3, comprising, as an additional layer, at least one gas barrier layer.
5. Laminated film according to claim 4, wherein the said gas barrier layer is formed from a copolymer of ethylene/vinyl alcohol (EVOH) or from polyv inylidenechloride.
6. Laminated film according to any of clalmsl to 5, wherein the said copolyamide layer has a thickness in the range of 3 to 50,u.
7. Laminated film according to any of claims 1 to 6, comprising a further surface layer of a said copolyamide having a thickness in the range of 10 to 1 00,a.
8. Laminated film according to claim 7, wherein the said further copolyamide layer is bioriented and heat-shrinkable.
9. Laminated film according to any of claims 1 to 8 further comprising at least one olefinic protective layer.
10. Laminated film according to any of the preceding claims, wherein the said multiple layers have 50 been at least in part united together by co-extrusion.
11. Laminated film according to any of claims 1 to 9, wherein the said multiple layers have been at least in part united together by the interposition of adhesive layers therebetween.
12. Laminated film according to claim 1 substantially as hereinbefore described.
13. A bag or other container suitable for packaging food to be subjected to heat treatment at a 55 temperature in the range of 700C to 1200C for a period of time from about 10 minutes to about 15 hours, the said container comprising a laminated film as claimed in any of claims 1 to 12.
1 el GB 2 129 370 A 5
14. A bag or other container as claimed in claim 13 adapted to be closed by heat-welding the said laminated film or by clipping.
15. Packaged food product comprising a container formed from a film according to any one of the. claims 1 to 12 and a food product which has been heat-treated within said container at 70-1206C for 5 a period from 15 hours to 10 minutes.
Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1984. Published by the Patent Office, Southampton Buildings, London, WC2A JAY, from which copies may be obtained.
c
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24051/82A IT1153003B (en) | 1982-11-03 | 1982-11-03 | LAMINATED FILMS FOR PACKAGING AND RELATED ITEMS WITH IMPROVED RESISTANCE TO HEAT TREATMENTS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8329340D0 GB8329340D0 (en) | 1983-12-07 |
| GB2129370A true GB2129370A (en) | 1984-05-16 |
| GB2129370B GB2129370B (en) | 1986-08-20 |
Family
ID=11211696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08329340A Expired GB2129370B (en) | 1982-11-03 | 1983-11-03 | Laminated packaging films and their use |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4568580A (en) |
| JP (1) | JPS5987154A (en) |
| AU (1) | AU565244B2 (en) |
| BE (1) | BE898132A (en) |
| BR (1) | BR8304964A (en) |
| CA (1) | CA1224129A (en) |
| CH (1) | CH663380A5 (en) |
| DE (1) | DE3339836C2 (en) |
| DK (1) | DK501283A (en) |
| ES (1) | ES526979A0 (en) |
| FI (1) | FI79807C (en) |
| FR (1) | FR2535249B1 (en) |
| GB (1) | GB2129370B (en) |
| IT (1) | IT1153003B (en) |
| MX (1) | MX163274B (en) |
| NL (1) | NL191205C (en) |
| NZ (1) | NZ205032A (en) |
| SE (1) | SE463297B (en) |
| ZA (1) | ZA835930B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0248585A1 (en) * | 1986-05-23 | 1987-12-09 | Kureha Kagaku Kogyo Kabushiki Kaisha | Heat-shrinking laminate film and process to produce the same |
| EP0382236A2 (en) * | 1989-02-10 | 1990-08-16 | The B.F. Goodrich Company | Polyamide laminated on thermoplastic polyurethane |
| EP0552911A1 (en) * | 1992-01-21 | 1993-07-28 | W.R. Grace & Co.-Conn. | Cook-in film with improved seal strength |
| US5700900A (en) * | 1992-12-24 | 1997-12-23 | Ems-Inventa Ag | Copolyamides with long-chain polyamide units |
| WO2000026024A1 (en) * | 1998-10-29 | 2000-05-11 | Cryovac, Inc. | New high resistance heat-shrinkable thermoplastic film |
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| US5006384A (en) * | 1985-11-29 | 1991-04-09 | American National Can | Films using blends of polypropylene and polyisobutylene |
| DK164495C (en) * | 1986-03-26 | 1992-11-23 | Kuraray Co | Multilayer structure with an oxygen barrier layer consisting of a blend of an ethylene-vinyl alcohol alcohol copolymer and an amide copolymer |
| US4729926A (en) * | 1986-05-16 | 1988-03-08 | W. R. Grace & Co., Cryovac Div. | Packaging material for long-term storage of shelf stable food products and method of making same |
| GB2197253B (en) * | 1986-11-14 | 1990-08-22 | Bcl Ltd | Multilayer carrier films |
| US4855183A (en) * | 1986-11-17 | 1989-08-08 | W. R. Grace & Co.-Conn. | Multiple-layer, cook-in film |
| DE3816942C2 (en) * | 1987-05-21 | 2000-06-15 | Gunze Kk | Food packaging material and manufacturing process therefor |
| DE3845009B4 (en) * | 1987-05-21 | 2004-03-11 | Gunze Ltd., Ayabe | Food packaging multilayer plastics film |
| US4977022A (en) * | 1988-03-15 | 1990-12-11 | W. R. Grace & Co.-Conn. | Barrier stretch film |
| US4939076A (en) * | 1988-03-15 | 1990-07-03 | W. R. Grace & Co.-Conn. | Barrier stretch film |
| US5213900A (en) * | 1990-03-23 | 1993-05-25 | W. R. Grace & Co.-Conn. | Cook-in film with improved seal strength |
| DK0676438T3 (en) * | 1991-10-28 | 2000-02-07 | Idemitsu Petrochemical Co | Easy-to-split oriented film and process for making it |
| US5618629A (en) * | 1991-12-27 | 1997-04-08 | Tokai Rubber Industries, Inc. | Flexible partition member for hydraulic accumulator, including ethylene-vinyl alcohol copolymer gas-barrier layer and polyamide resin elastic layer |
| FR2685740B1 (en) * | 1991-12-27 | 1994-08-12 | Tokai Rubber Ind Ltd | FLEXIBLE SEPARATION ELEMENT FOR A HYDRAULIC ACCUMULATOR COMPRISING A GAS STOPPER LAYER IN VINYL ETHYLENE-ALCOHOL COPOLYMER AND AN ELASTIC LAYER IN POLYAMIDE RESIN. |
| US5252155A (en) * | 1992-03-10 | 1993-10-12 | National Starch And Chemical Investment Holding Corporation | Shrink film labeling with polyurethane hot melts |
| US5298326A (en) * | 1992-03-27 | 1994-03-29 | W. R. Grace & Co.-Conn. | Cook in film with improved seal strength and optics |
| US5698279A (en) * | 1992-09-23 | 1997-12-16 | Viskase Corporation | Heat shrinkable nylon food casing having a functionalized ethylenic polymer core layer |
| US5843502A (en) * | 1996-06-26 | 1998-12-01 | Cryovac, Inc. | Package having cooked food product packaged in film having food adhesion layer containing high vicat softening point olefin/acrylic acid copolymer |
| EP0918635B1 (en) * | 1996-08-16 | 2002-12-04 | Cryovac, Inc. | Article comprising film having polyamide sealant, polyamide core layer, and o 2-barrier layer, and packaged product using same |
| US5840825A (en) * | 1996-12-04 | 1998-11-24 | Ppg Incustries, Inc. | Gas barrier coating compositions containing platelet-type fillers |
| US5728439A (en) * | 1996-12-04 | 1998-03-17 | Ppg Industries, Inc. | Multilayer packaging material for oxygen sensitive food and beverage |
| DE69826320D1 (en) | 1997-12-30 | 2004-10-21 | Cryovac Inc | MULTILAYER FILM FOR GOODS COOKED IN THE PACKAGING |
| AU5214901A (en) * | 2000-03-13 | 2001-09-24 | Cryovac Inc | Bi-axially oriented and heat-set multilayer thermoplastic film for packaging |
| US20040086551A1 (en) * | 2002-10-30 | 2004-05-06 | Miller Kenneth J. | Fentanyl suspension-based silicone adhesive formulations and devices for transdermal delivery of fentanyl |
| GB2437491A (en) * | 2006-04-11 | 2007-10-31 | O Pro Mouthguards | Mouthguard including projections to improve moulding |
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- 1983-07-27 NZ NZ205032A patent/NZ205032A/en unknown
- 1983-07-29 AU AU17436/83A patent/AU565244B2/en not_active Expired
- 1983-08-11 ZA ZA835930A patent/ZA835930B/en unknown
- 1983-08-17 MX MX198428A patent/MX163274B/en unknown
- 1983-08-31 NL NL8303033A patent/NL191205C/en not_active IP Right Cessation
- 1983-09-14 BR BR8304964A patent/BR8304964A/en unknown
- 1983-09-19 US US06/533,190 patent/US4568580A/en not_active Expired - Lifetime
- 1983-09-23 CA CA000437413A patent/CA1224129A/en not_active Expired
- 1983-09-26 SE SE8305188A patent/SE463297B/en not_active IP Right Cessation
- 1983-10-11 JP JP58188560A patent/JPS5987154A/en active Granted
- 1983-10-28 BE BE0/211808A patent/BE898132A/en not_active IP Right Cessation
- 1983-10-31 CH CH5885/83A patent/CH663380A5/en not_active IP Right Cessation
- 1983-10-31 FI FI833988A patent/FI79807C/en not_active IP Right Cessation
- 1983-11-01 DK DK501283A patent/DK501283A/en not_active Application Discontinuation
- 1983-11-01 DE DE3339836A patent/DE3339836C2/en not_active Revoked
- 1983-11-02 ES ES526979A patent/ES526979A0/en active Granted
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0248585A1 (en) * | 1986-05-23 | 1987-12-09 | Kureha Kagaku Kogyo Kabushiki Kaisha | Heat-shrinking laminate film and process to produce the same |
| US4892765A (en) * | 1986-05-23 | 1990-01-09 | Kureha Kagaku Kogyo Kabushiki Kaisha | Heat-shrinkable laminate film and process to produce the same |
| EP0382236A2 (en) * | 1989-02-10 | 1990-08-16 | The B.F. Goodrich Company | Polyamide laminated on thermoplastic polyurethane |
| EP0382236A3 (en) * | 1989-02-10 | 1991-03-06 | The B.F. Goodrich Company | Polyamide laminated on thermoplastic polyurethane |
| EP0552911A1 (en) * | 1992-01-21 | 1993-07-28 | W.R. Grace & Co.-Conn. | Cook-in film with improved seal strength |
| US5700900A (en) * | 1992-12-24 | 1997-12-23 | Ems-Inventa Ag | Copolyamides with long-chain polyamide units |
| WO2000026024A1 (en) * | 1998-10-29 | 2000-05-11 | Cryovac, Inc. | New high resistance heat-shrinkable thermoplastic film |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA835930B (en) | 1984-04-25 |
| JPS5987154A (en) | 1984-05-19 |
| BR8304964A (en) | 1984-11-06 |
| BE898132A (en) | 1984-02-15 |
| SE8305188L (en) | 1984-05-04 |
| FI79807B (en) | 1989-11-30 |
| MX163274B (en) | 1992-03-31 |
| IT1153003B (en) | 1987-01-14 |
| AU1743683A (en) | 1984-05-10 |
| NL191205C (en) | 1995-03-16 |
| FR2535249A1 (en) | 1984-05-04 |
| CH663380A5 (en) | 1987-12-15 |
| GB8329340D0 (en) | 1983-12-07 |
| DE3339836C2 (en) | 1997-07-17 |
| GB2129370B (en) | 1986-08-20 |
| NZ205032A (en) | 1986-12-05 |
| DE3339836A1 (en) | 1984-06-07 |
| NL191205B (en) | 1994-10-17 |
| FI833988A0 (en) | 1983-10-31 |
| DK501283A (en) | 1984-05-04 |
| IT8224051A0 (en) | 1982-11-03 |
| DK501283D0 (en) | 1983-11-01 |
| NL8303033A (en) | 1984-06-01 |
| CA1224129A (en) | 1987-07-14 |
| JPH0410420B2 (en) | 1992-02-25 |
| ES8406952A1 (en) | 1984-09-01 |
| FI833988A (en) | 1984-05-04 |
| SE8305188D0 (en) | 1983-09-26 |
| FI79807C (en) | 1990-03-12 |
| ES526979A0 (en) | 1984-09-01 |
| US4568580A (en) | 1986-02-04 |
| SE463297B (en) | 1990-11-05 |
| FR2535249B1 (en) | 1986-12-26 |
| AU565244B2 (en) | 1987-09-10 |
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| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20011103 |